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Amines
Part-01

Amines can be considered as derivatives of ammonia obtained by replacement of one, two or all the three
hydrogen atoms by alkyl/aryl groups.

Classification of Amines
Amines are classified according to the number of carbon atoms bonded directly to the nitrogen atom.

Methods of Preparation of amines

1. Reduction of nitro compounds
Nitro compounds are reduced to amines by passing hydrogen gas in the presence of finely divided nickel,
palladium or platinum and also by reduction with metals in acidic medium.

2. Reduction of nitriles(cyanides) and isonitriles (isocyanides)

Nitriles on reduction with lithium aluminium hydride (LiAlH4) or catalytic hydrogenation produce primary amines
but isonitriles produce secondary amines.

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Amines Part-01

3. Reduction of amides
Amides on reduction with lithium aluminium hydride (LiAlH4) produce amines.

4. Ammonolysis of alkyl halides

Alkyl halide on reaction with ethanolic solution of ammonia undergoes nucleophilic substitution in which the
halogen atom is replaced by amino (-NH2) group. The process of cleavage of C-X bond by ammonia is known
as Ammonolysis.
NH3 + R—X ⎯→ R—NH2

Ammonolysis reaction yields a mixture of primary, secondary, tertiary amines and also quaternary ammonium
salt. However primary amine can be obtained as major product taking large excess of ammonia and quaternary
ammonium salt will be major product if alkyl halide is taken in excess.

5. Gabriel phthalimide synthesis

Gabriel synthesis is used for the preparation of 1° aliphatic amines.
Phthalimide on treatment with ethanolic potassium hydroxide forms potassium salt of phthalimide which on
reaction with alkyl halide followed by alkaline or acidic hydrolysis produces the corresponding primary amine.

Mechanism

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Amines
Part-02

Methods of Preparation of amines

6. Hoffmann bromamide degradation reaction

Reagents that may be used for this reaction

1. X2 + alkaline medium
Br2 + NaOH
Br2 + KOH
2. NaOX (NaOCl, NaOBr etc.)
KOX (KOCl, KOBr etc.)

Physical Properties of Amines

Solubility
1. Lower aliphatic amines are soluble in water because they can form hydrogen bonds with water molecules.
2. Solubility decreases with increase in molar mass of amines due to increase in size of the hydrophobic alkyl part.
3. Higher amines are essentially insoluble in water.

Boiling point
Primary and secondary amines are engaged in intermolecular association due to hydrogen bonding between
nitrogen of one and hydrogen of another molecule.

This intermolecular association is more in primary amines than in secondary amines as there are two hydrogen
atoms available for hydrogen bond formation in it.

Tertiary amines do not have intermolecular association due to the absence of hydrogen atom required for
hydrogen bond formation.

The order of boiling points of isomeric amines is as follows:

Primary > Secondary > Tertiary

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Amines Part-02

Chemical reactions of Amines

(1) Reaction showing basic nature
Amines being basic in nature react with acids to form salts.

Amine salts on treatment with a base like NaOH, regenerate the parent amine.

(2) Acylation reaction

Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and esters by
nucleophilic substitution reaction.

(3) Hoffmann's carbylamine reaction or isocyanide test

Aliphatic and aromatic primary amines on heating with chloroform and ethanolic potassium hydroxide form
isocyanides or carbylamines which are foul smelling substances.

Note: Dichlorocarbene is formed in this reaction.

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Amines
Part-03

Chemical reactions of Amines

(4) Reaction with Benzenesulphonyl chloride (Hinsberg’s reagent)

Note:
Hinsberg test is used to distinguish between primary, secondary and tertiary amines.
These days benzenesulphonyl choride is replaced by p-toluenesulphonyl chloride (TsCl)

(5) Reaction with nitrous acid (HNO2)

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Amines Part-03

(a) 1° Aliphatic amine

Mechanism

(b) 1° Aromatic amine

If the temperature of the diazonium salt solution is allowed to rise upto 283K, the salt gets hydrolysed to phenol.

(c) 2° Aromatic amine

(d) 3° Aromatic amine

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Amines Part-03

Chemical reaction of Diazonium salts

A. Reactions involving displacement of nitrogen

B. Reactions involving retention of diazo group

Coupling reaction of benzene diazonium chloride (ESR)
Benzene diazonium chloride reacts with aromatic compounds containing strongly activating groups like
–OH, –NH2, –NHR, –NR2

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Amines
Part-04

Chemical reactions of Amines

(6) Electrophilic Substitution Reaction (ESR)
Halogenation of Aniline

Nitration of Aniline

Illustration

Sulphonation of Aniline

Note:
Aniline does not show Friedel Crafts reaction (alkylation and acylation)

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Amines Part-04

Reduction of Nitrobenzene

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